Aerosol germicide and dye

ABSTRACT

An aerosol spray for use in disinfecting a surface for personal use, such as a public restroom facility or telephone. The composition and delivery of the composition provides for the placement of a spray of disinfectant which includes a dye. The dye disappears as the spray effects the germicidal activity of the disinfectant. The composition is also rapidly drying, so that the dye disappears as well as the disinfecting composition leaving the surface dry.

BACKGROUND OF THE INVENTION

This application is a continuation-in-part of U.S. Ser. No. 738,082filed May 24, 1985, now abandoned, for "Germicide and Dye Compositionand Method."

In an effort to protect the public from unsanitary surfaces in publicrestrooms, telephones and other surfaces which are contacted by thepublic a number of methods have been developed. Many people have anaversion to using public restroom facilities or other objects forpersonal use which have been used previously by others. With theincreased concerns of Herpes simplex virus type 2 which is a persistentviral infection once contracted, the community has become increasinglycautious about exposure.

One of the more commonly available methods for protection is adisposable paper cover for the toilet facility. The paper covers do notcontain a germicide and are not always available.

A spray germicide for sanitizing surfaces which is quick drying wasdisclosed in U.S. Pat. No. 3,445,564 to Kirscher. The patent discloses aspray and other alternative embodiments of a quick drying germicide. Itdoes not disclose effectiveness against Herpes or the range of pathogensdisclosed herein. Also, there is no disclosure of use of thedisappearing dye which provides a visual assurance and confirmation ofthe area treated as well as an indicator of germicidal destruction.

The use of a dye in a bacteriacidal solution was disclosed in U.S. Pat.No. 2,449,274 to Broll. The use of the dye was in a bacteriacidal liquidto clean objects such as tableware. The solution would change color uponlosing bacteriacidal strength. This was not a surface spray applicationwith a dye indicator.

There are a number of applications for spray germicides such as thecommercially available Lysol® spray by Lehn and Fink Products Divisionof Sterling Drug, Inc. U.S. Pat. Nos. 3,282,776 and 4,201,764 areexamples of surface or surface and space spray combinations. None of thepatents or products include a dye which is used with the spray in anymanner.

SUMMARY OF THE INVENTION

The purpose of this invention is to provide a germicidal compositionwith a disappearing dye which can be dispersed in a fine spray with thedye indicating the delivery of the germicide. Although the dye is addedfor color, it is thoroughly mixed and completely dispersed in the systemso that a coating or fine layer of spray imparts the visual coloredcomposition will also indicate an active germicidal coating or layer.The germicide is effective against Herpes simplex virus type 2 (HSV2) aswell as bacteria such as Staphylococcus aureus, Neisseria gonorrhoeae,enteric bacteria Escherichia coli 011K58 (Pathogenic), Shigella sonneiand Salmonella typhimurium, and the yeast Candida albicans. The dye willbe quite noticeable on lighter colored surfaces and therefore give avisual check as to the area disinfected. It is believed a novel spraywith a dye included will enhance usage by the consumer.

Another aspect of the germicide is to provide one or move detergents asgermicides. The detergents are surface active and attack the targetpathogen but also, through the surface active qualities, causes thespray to spread effectively on the surface to be disinfected. Thespreading aspect is especially helpful because the individual dropletsdispensed from any type of spray device will spread to provide a moreeven layer before drying. In addition to the delivery of an effectivegermicide for a broad range of organisms with a dye, the composition isalso quick drying.

The composition can be packaged in any type of airtight container suchas an aerosol spray and can be made in a convenient size which can becarried in a purse or pocket. The composition can also be packaged in alarger size spray dispenser for multiple applications for home orcommercial use.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The product is manufactured as a fluid which is packaged in an aerosolspray dispensing unit for personal or home use in the appropriate sizeof container. An aliphatic alcohol with high volatility is used as theprimary component by volume. The alcohol has bacteriacidalcharacteristics and allows for the rapid drying of the layer ofdisinfectant sprayed on the surface. For use in public restrooms arapidly drying composition would be most desirable for use. Due to costand availability, isopropanol is utilized in the examples although otherquick-drying alcohols could be substituted. The isopropanol can be mixedwith an amount of water and the examples show about a 70% isopropanolmixture with 30% water.

Disinfecting surfactant-detergent compounds are also used in the fluidcomposition. Surfactants are effective germicides and attack themembranes of the organisms. Also, the surfactants are surface activereducing surface tension. This phenomena causes the spreading over thesurface of the disinfecting composition providing a more effectivedistribution of the germicide spray on the surface. It is thought thatthe surfactant has two characteristics which contribute to thisinvention. Those being germicidal activity including effectiveness overa wide range of organisms including bacteria, virus and yeast andproviding a reduction of the surface tension of the composition toachieve effective spread and distribution if the germicide on thesurface to be disinfected. Two different types of surfactants weretested separately and in combination for efficacy. It was found thatboth sodium dodecyl sulfate and octyl phenoxy polyethoxyethanol areeffective germicide-surfactants. There are other compounds which havethe properties of germicide-surfactants, and this invention is notlimited to those compounds shown in the examples.

The composition contains a dye which is dissolved and dispersed in thecomposition. In the examples, the dye selected is a pH indicator bluedye which is colored at alkaline pH and upon neutralization becomescolorless. The blue dye was chosen for the examples because of a cleanassociation by the public with the blue color. Any other dye color couldbe used which would be acceptable for a particular use. Other indicatorswhich have the similar pH sensitivity can be used as shown, for instancein the Table of "Indicators for Volumetric Work and pH Determination" inthe Merck Index 10th Ed. (1983).

The composition of the examples has the pH adjusted with the addition ofan alkali such as sodium hydroxide so that the blue color is deep andnoticeable when applied, but losing color upon use. The pH sensitive dyewas chosen for use by the public because the delivery of the alkalinecomposition in the environment causes the color to change in a shortperiod of time. The color change is probably due to the neutralizationof the composition from CO₂ in the air and the surface on which it issprayed. The alkalinity of the material is adjusted carefully so thatthe neutralization of the composition can produce a visual change fromblue to clear within a short period of time. During the neutralizationof the composition and visible change of color, the alcohol surfactantgermicide is producing an effective kill on organisms present. Thedisappearance of the color, the killing of the organisms, and the dryingof the germicide occur in rapid sequence leaving a dry, germ-freesurface for personal use.

It is also found that this composition does not leave a film afterdrying so that the surface is not tacky and undesirable for personaluse. Also, the composition does not have an objectionable odor as foundin phenolic type germicides. Perfume additives may be used to provide afragrance if desired but are not necessary to mask the odor of thegermicidal composition.

There is a factor of the necessity of an airtight container for a pHsensitive dye. If ambient air is allowed to penetrate into thecontainer, the liquid may be neutralized and the color will disappear.Also, the highly volatile alcohol will escape if the container is notsealed. The disappearance of the color will not affect the strength ofthe germicide detergent which have a long shelf life.

For personal use a small aerosol container which delivers a fine sprayis a practical packaging for the composition. For commercial packaging ahydrocarbon propellant is preferable to meet environmental qualitystandards. For testing a fluorocarbon propellant of the Freon type wasused. A propellant system to deliver a fine spray is preferable becauseit will deliver a fine, rapidly spreading layer which will dry quickly.Atomizers or other devices which deliver a denser spray may necessitatethe wiping of the composition with toilet paper or other wipe before usebecause of a longer evaporation time for a dense spray. Anotherpreparation of the invention can be the saturation of a woven wipe whichis sealed in a foil or other airtight packaging. The packet would betorn open for a one-time usage of the wipe delivering the dye coloredgermicide to the surface. The rubbing of the wipe on the surface willpromote evaporation of the composition.

EXAMPLE I

A sample of the germicidal composition was prepared by adding 400 mg ofsodium dodecyl sulfate (SDS) and 400 of octyl phenoxy polyethoxyethanolmarketed as Triton X-100 a product of Sigma Chemical Company to 100 mlof 70% by volume isopropanol. 100 mg of blue dye thymophthalein wasadded. The pH was adjusted with 0.05 ml of 12N NaOH which produces adeep blue colored liquid when keep air tight. This also gave a pH of12.53 to the liquid. When the composition is allowed to stand exposed toair it becomes colorless and the pH drops to 8.8. Tests were done onadjusting the pH with the blue dye thymophthalein and it was found thatthe dark blue color is present at about 11.27 pH. A lighter blue ispresent at 11.01 pH and the liquid is clear at 10.95 pH and lower. Aninitial dark blue was used in Example 1 to produce a colored spray.However, the NaOH added was not excessive to prevent bleaching when thecomposition is exposed as a spray or thin coating on a surface in thenormal atmosphere.

This composition was tested for germicide effectiveness against Herpessimplex virus type 2 (HSV2), Neisseria gonorrhoeae, Staphylococcusaureus, Escherichia coli 011K58, Shigella sonnei, Salmonellatyphimurium, and Candida albicans. The composition was sprayed anddropped on pathogen suspensions to test efficacy and dye colordisappearance.

In both the spray and drop tests 0.1 milliliters (ml) of test pathogenicorganisms containing approximately 1×10⁷ organisms were placed on thesurface of a sterile plastic Petri dish. In the drop test 0.1 ml of thecomposition of Example I was added by pipette to the pathogen suspensionin the Petri dish. The pathogen suspension and drop of Example I weremixed and allowed to stand for twenty seconds. The blue color woulddisappear before the twenty seconds elapsed. At the end of twentyseconds the Petri plate was tilted and 0.1 ml of the test sample wasremoved. In the spray test the composition of Example I was placed in anaerosol spray with a fluorocarbon propellant. The 0.1 ml of thepathogenic organism suspension in the Petri plate was sprayed for twoseconds with Example I. It was determined that between 0.6 and 0.9 ml ofliquid was delivered in the two second spray. The spray spreads quitenoticeably over the Petri plate and the blue color disappears in a shorttime. The spray was allowed to mix on the Petri plate for twentyseconds. After twenty seconds the Petri plate was tilted and 0.1 ml ofthe sample was removed for testing.

The test samples removed from the drop and spray tests were diluted andplated on agar medium (casman media for S. typhimurium, S. sonnei and E.coli; chocolate agar supplemented with factor XV for N. gonorrhoeae, andsheep blood agar for S. aureus and C. albicans). HSV2 was added to thefirst wells of a 96-well sterile microtiter tissue culture plate,serially diluted and cultured with VERO monkey kidney cells for fivedays. Phosphate buffered saline was used as a diluent for all organismsexcept N. gonorrhoeae and HSV2; phosphate buffered saline (PBS)containing 0.5% gelatin was used as a diluent for the N. gonorrhoeae andminimal essential medium supplemented with 5% fetal calf serum andantibiotics was used for the HSV2. Each test included a control(pathogenic organism+diluent) and a quantitative titration of thepathogen to determine the actual number of organisms in each testsuspension. All Petri and tissue culture plates were incubated in 37° C.(5% CO₂) incubators.

All Petri plates were observed the morning after plating for colonyforming units (CFU) and the number of organisms present in the testsuspensions were calculated. The tissue culture plates containing VEROcells were observed daily for virus specific cytopathic effects (CPE).At the end of five days the last well in each series of dilutionsshowing CPE was recorded and the tilter of virus in the original testsuspensions calculated. Each assay involving HSV2 had a tissue culturecontrol (VERO cells+media only) and a virus control (VERO cells+HSV2 andno germicide).

The results of the cidal activity of Example I are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        The Microcidal Activity of Example I                                          Against Various Pathogens.                                                               No.    Mean                                                                   of     Percent                                                     Pathogen   tests  killing  Range Comments                                     ______________________________________                                        S. aureus  6       >99*    99-99.9                                                                             Similar killing                                                               by drop or spray.                            C. albicans                                                                              6      >99      99-99.9                                                                             Similar killing                                                               by drop or spray.                            N. gonorrhoeae                                                                           5      >99      99-99.9                                                                             Similar killing                                                               by drop or spray.                            E. coli 011K58                                                                           3      >99      99-99.9                                                                             Similar killing                                                               by drop or spray.                            S. sonnei  3      >99      99-99.9                                                                             Similar killing                                                               by drop or spray.                            S. typhimurium                                                                           3      >99      99-99.9                                                                             Similar killing                                                               by drop or spray.                            HSV2       5       99      99-99 Similar killing                                                               by drop or spray;                                                             may be > than 99%                                                             killing but toxi-                                                             city of Example I                                                             to VERO cells                                                                 made lower dilu-                                                              tions unreadable.                            ______________________________________                                         *Percent killing was determined by dividing the total number of viable        organisms in suspensions exposed to Example I by the total number of          viable organisms in suspensions exposed to phosphate buffered saline and      multiplying by 100.                                                      

Example I was compared to Lysol for strength of killing the organismsHSV2, S. aureaus, N. gonorrhoeae. E. coli 011K58, S. typhimurium, S.sonnei and C. albicans, the complete range of pathogens testedpreviously. The test was conducted for spray delivery. Example I wasfound to compare with the percentage kill equivalent to Lysol in a sideby side test.

The composition was diluted to determine efficacy. Distilled water waschosen as the dilutant because PBS caused a cloudy liquid and additionalalcohol would affect germicidal properties. There was a noticeabledecrease in surface tension reduction decreasing the spreading of thecomposition with a tenfold dilution with water. After a 100-folddilution with water, no reduction in surface tension was seen. Thekilling effect of the dilutions of this example are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    The Microcidal Effect of Different Dilutions of                               Example I Against Various Pathogens.                                                  No.                                                                           of Percent of killing at dilution                                     Pathogen                                                                              tests                                                                            0        10-fold                                                                              100-fold                                                                           1000-fold                                     __________________________________________________________________________    S. aureus                                                                             3   >99/>99/>99*                                                                          37/90/99                                                                             8/54/90                                                                            20/75/ND**                                    C. albicans                                                                           3  >99/>99/>99                                                                            40/13/95                                                                             0/53/25                                                                            0/0/ND                                        N. gonorrhoeae                                                                        3  >99/>99/>99                                                                            >99/72/90                                                                            0/74/92                                                                            15/0/79                                       HSV2    2  99/99    99/99  0/7  0/7                                           __________________________________________________________________________     *Results of replicate experiments are separated by slant (/) bars.            **ND = not done.                                                         

EXAMPLE II

Another embodiment of the composition can be made using SDS as the onlysurfactant-germicide. The composition was prepared as described inExample I omitting the addition of Triton X-100 and using 400 mg of SDSas the only surfactant-germicide. Testing the cidal activity of ExampleII on the organisms listed in Table 3 below was carried out aspreviously outlined in Example I.

                  TABLE 3                                                         ______________________________________                                        The Microcidal Effect of Example II.                                                     No.                                                                           of       % Killings                                                Organism     Tests      Spray   Drop                                          ______________________________________                                        HSV2         2           99      99                                           N. gonorrhoeae                                                                             2          >99     >99                                           S. aureas    2          >99     >99                                           C. albicans  2          >99     >99                                           ______________________________________                                    

EXAMPLE III

An alternate embodiment of the composition can be made using TritonX-100 as the only surfactant-germicide. The composition was prepared asdescribed in Example I omitting SDS and adding 400 mg of Triton X-100 asthe only surfactant-germicide. Testing on the organisms listed in Table4 below was carried as previously outlined in Example I.

                  TABLE 4                                                         ______________________________________                                        The Microcidal Effect of Example III.                                                      No.                                                              Example      of         % Killings                                            Organism     Tests      Spray   Drop                                          ______________________________________                                        HSV2         2           99      99                                           N. gonorrheae                                                                              3          >99     >99                                           S. aureas    3          >99     >99                                           C. albicans  3          >99     >99                                           ______________________________________                                    

EXAMPLE IV

A formula for use with a hydrocarbon propellant is shown in thefollowing Table 5.

                  TABLE 5                                                         ______________________________________                                        Biocide and Hydrocarbon Propellant                                            Ingredient        Weight %                                                    ______________________________________                                        Isopropanol       51.62                                                       Dionized Water    27.52                                                       Triton X-100      0.38                                                        TEA-Lauryl Sulfate                                                                              0.38                                                        Thymolphthalein   0.10                                                        Aeropin-70 Propellant                                                                           20.00                                                       ______________________________________                                    

In this example, Triethanol Amine Lauryl Sulfate was used. TheComposition is adjusted to pH 11.5 with 10% NaOH. The Aeropin-70 is ahydrocarbon propellant of the following composition in Table 6.

                  TABLE 6                                                         ______________________________________                                        Hydrocarbon Propellant                                                        Liquid Volume %   Molecular % Weight %                                        ______________________________________                                        Propane 51.05         54.79       47.92                                       Isobutane                                                                             19.81         17.84       20.61                                       N--butane                                                                             29.14         27.32       31.47                                       ______________________________________                                    

The propellant system used can be any environmentally acceptable spraythat disperses the biocide in a fine layer.

As seen from the result of testing on a wide range of pathogens, acomposition containing one or more surfactant-germicide provides veryeffective killing strength used as a drop or spray. Various othersurfactants could be substituted as the surfactant-germicide and it isnot the intent of the invention to limit the compounds used.

What is claimed is:
 1. A biocide aerosol spray dispensing unit fordisinfecting a surface with a fine spray consisting essentially ofafluid biocide; a sufficiently airtight container for said fluid biocide;said fluid biocide including a lower alkyl alcohol having 1 to 4 carbonatoms, an effective amount of a disinfecting surfactant, a pH sensitivedye, and alkali means for adjusting the pH of the fluid to produce acolor in the liquid in the dye so that upon neutralization the dye losescolor; and a propellant system to disperse a fine spray of said biocideon the surface to be disinfected.
 2. A biocide aerosol of claim 1wherein said pH sensitive dye is an indicator which is colored in thealkali state and loses color when dispersed as a fine spray uponoxidation in the atmosphere.
 3. A biocide aerosol of claim 1 whereinsaid alcohol is mixed with water up to about 30% of water.
 4. A biocideaerosol of claim 1 wherein said alcohol is isopropanol.
 5. A biocideaerosol of claim 1 wherein said disinfecting surfactant is selected fromthe group of sodium dodecyl sulfate, octyl phenoxy polyethoxyethanol,triethanol amine lauryl sulfate and mixtures thereof.
 6. A biocideaerosol of claim 1 wherein said propellant is selected from afluorocarbon or hydrocarbon propellant.
 7. A biocide aerosol of claim 1with a fragrance additive.